Oxyalkylated aliphatic polyepoxidetreated amine-modified phenol aldehyde resins, andmethod of making same



United States Patent OXYALKYLATED ALIPHATIC POLYEPOXIDE- TREATED AMINE-MODIFIED PHENOL ALDE- glYDE RESINS, AND .METHOD OF MAKING AME Melvin De Groote, St. Louis, and Kwan-Ting Shen, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Original application July 30, 1953, Serial No. 371,410, now Patent No. 2,771,451, dated November 20, 1956. Divided and this application September 12, 1956, Serial No. 609,355

7 Claims. 01. 26045) The present invention is a continuation-in-part of our co-pending application, Serial No. 364,501, filed June 26, 1953, now U. S. Patent 2,771,425, and a division of our co-pending application Serial No. 371,410, filed July 30, 1953, now U. S. Patent 2,771,451.

Our invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleumemulsions. Our invention is also concerned with the application of such chemical products or compounds in various other arts and industries as well as with method of manufacturing the new chemical products of compounds which are of outstanding value in demulsification.

The present invention is concerned with a three-step manufacturing method involving (1) condensing certain phenol aldehyde resins, hereinafter described in detail, with certain basic non-hydroxylated secondary monoamines, hereinafter described in detail, and formaldehyde; (2) oxyalkylation of the condensation product with certain nonaryl hydrophile polyepoxides hereinafter described in detail; and (3) oxyalkylation ofthe previously oxyalkylated resin condensate with certain mono epoxides, also hereinafter described in detail.

The present invention is characterized by analogous compounds derived from diglycidyl ethers which do not introduce any hydrophobe properties in its usual meaning but, in fact, are more apt to introduce hydrophile properties. Thus, the diepoxides employed in the present invention are characterized by the fact that the divalent radical connecting the terminal epoxide radicals contains less than 5 carbon atoms in an uninterrupted chain.

The diepoxides employed in the present process are obtained from glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, diglycerol, triglycerol, and similar compounds. Such products are well known and are characterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which is part of the radical joining the epoxide groups. Of necessity such diepoxides must be nonaryl or aliphatic in character. The diglycidyl ethers of co-pending application, Serial No. 364,501, are invariably and inevitably aryl in character.

The diepoxides employed in the present process are usually obtained by reacting a glycol or equivalent compound, such as glycerol or diglycerol, with epichlorohydrin and subsequently with an alkali. Such diepoxides have been described in the literature and particularly the patent literature. See, for example, Italian Patent No. 400,973, dated August 8, 1951; see, also, British Patent 518,057, dated December 10, 1938; and U. S. Patent No. 2,070,990, dated February 26, 1937 to Gross et al. Reference is made also to U. S. Patent 2,581,464, dated Janu- 7 ary 8, 1952, to Zech. This particular last mentioned patent describes a composition of the following general formula:

O -(ilHz-CHO CHrCHg 10 Halogen" v "2' in which x is at least 1, z varies from less than 1 to more than 1, and x and 1 together are at least 2 and not more than 6, and R is the residue of the polyhydric alcohol'remaining after replacement of at least 2 of the hydroxyl groups thereof with the epoxide ether groups of the above formula, and any remaining groupsof the residue being free hydroxyl groups. I

It is obvious from what is said in the patent that variants can be obtained in which the halogen is replaced by a hydroxyl, radical; thus, the formula would become Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents suchas alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it sometimes is desirable to dilute the compound containing the epoxy rings before reacting with an amine condensate. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation as, for example, kerosene, benzene, 5 toluene, dioxane, possibly various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol. 1

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to means the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has 60 two or more oxirane rings they will be referred to'as polyepoxides. They usually represent, of course, 1,2;

epoxide rings or oxirane rings in the 21lpha-omega'position. This is a departure, of course, from the stand-point of strictly formal nomenclature as in the exampleof the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane- (1,2,3,4 diepoxybutane). 1

It well may be that even though the previously suggested formula represents the principal component, or 0 components, of the resultant or reaction product described in the previous text, it may be important. to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric compounds containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule. and may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent. in the usual thermosetting resins. Simply for the purpose of illustration to show a typical diglycidyl ether of the kind herein employed, reference is made to the following formula:

or if derived from cyclic diglycerol the. structure would be thus:

or the equivalent compound wherein the ring structure involves only 6 atoms, thus:

Commercially available compounds seem to be largely the former with comparatively small amounts, in fact, comparatively minor amounts, of the latter.

Having obtained a reactant having generally 2 epoxy rings as depicted in the next to last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenolaldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which are part of the phenolic nuclei and there may be present reactive hydrogen atoms attached to a nitrogen atom, or an oxygen atom, depending on the presence of a hydroxylated group or secondary'amino group.

.To illustrate the products which represent the subject matter of the present invention reference will be made to a, reaction involving a mole of the oxyalkylating agent, i. e.,the compound having two oxirane rings and an amine condensate. Proceeding with the example previously described it is obvious the reaction ratio of two moles of the amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

in which n' is a small whole number less than 10, and usually less than 4, and including O, and R represents a divalent radical as previously described bring free from any radical having more than 4 uninterrupted carbon atoms in a single chain, and the characterization condensate is simply an abbreviation for the condensate which is described in greater detail subsequently.

Such intermediate product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochoric acid, acetic acid, hydroxyacetic acid, gluconic acid, etc. In other words, the nitrogen groups present, whether two or more, may be or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in the instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to differentiate from instances where an insoluble material is desired but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to 20 times their weight of 5% gluconic acid at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, parts of xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone.

A mere examination of the nature of the products before and after treatment with a polyepoxide reveals that the polyepoxide by and large introduces increased hydrophile character or, inversely, causes a decrease in hydrophobe character. However, the solubility characteristics of the final product, i. e., the product obtained by oxyalkylation with a monoepoxide, may vary all over the map, This is perfectly understandable because ethylene oxide, glycide, and to a lesser extent methyl glycide, introduce predominantly hydrophile character, while propylene oxide and more especially butylene oxide, introduce primarily hydrophobe character. A mixture of the various oxides will produce a, balancing in solubility characteristics or in the hydrophobe-hydrophile character so as to be about the same as prior to oxyalkylation with the monoepoxide.

The oxyalkylated polyepoxide treated condensates obtained in the manner described are, in turn, oxyalkylation-susceptible and valuable derivatives can be obtained by further reaction with other alkylene oxides, for instance, styrene oxide (phenylethylene oxide), cyclohexylethylene oxide, ethylene imine, propylene imine, acrylonitrile, etc.

Similarly, the oxyalkylated polyepoXide-clerivcd compounds can be reacted with a product having both a nitrogen group and a 1,2-epoxy group, such as.3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated August 22, 1950, to Gross.

Although the herein described products. have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as Wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides; emulsifying agents, as, for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxyacetate, have sufficiently hydrophile character to at least meet the test set forth in U. S. Patent No, 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethyleneglycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided into eight parts:

Part 1 is concerned with the hydrophile nonaryl polyepoxides and particularly diepoxides employed as reactants;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation to yield the amine-modified resin;

Part 3 is concerned with appropriate basic secondary amines free from a hydroxyl radical which may be employed in the preparation of the herein-described aminemodified resins;

Part 4 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to reaction with polyepoxides, and particularly diepoxides;

Part 5 is concerned with reactions involving the two preceding types of materials and examples obtained by such reaction. Generally speaking, this involves nothing more than reaction between 2 moles of a previouslyprepared amine-modified phenol-aldehyde resin condensate as described and one mole of a hydrophile polyepoxide so as to yield a new and larger resin molecule, or comparable product;

Part 6 is concerned with the use of a monoepoxide in oxyalkylating the products described in Part 5, preceding, i. e., those derived by means of reaction between a polyepoxide and an amine-modified phenol-aldehyde resin as described;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 8 is concerned with uses for the products herein described, either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 Reference is made to previous patents as illustrated in the manufacture of the nonaryl polyepoxides and particularly diepoxides employed as reactants in the instant invention. The simplest diepoxide is probably'the one derived from 1,3-butadiene or isoprene. Such derivatives are obtained by the use of peroxides or by other suitable means and the diglycidyl ethers may be indicated thus:

H H H H W U O 0 CH3 H H H 0 0 v In some instances the compounds are essentially derivatives of etherized epichlorohydrin or methyl epichlorohydrin. Needless to say, such compounds can be derived from glycerol monochlorohydrin by etherization prior to ring closure. An example is illustrated'in. the previously mentioned Italian Patent No. 400,973:

CHZCHCH2O-CH2CHCHI O 0 Another type of diepoxide is diisobutenyl dioxide as described in aforementioned U. S. Patent No. 2,070,990; dated February 16, 1937, to Groll, and is of the following formula The diepoxides previously described may be indicated by the following formula:

H R R H H0C[R"],.,-0-GH in which R represents a hydrogen atom or methyl radical and R" represents the divalent radical uniting the two termina epoxide groups, and n is the numeral 0 or 1. As previously pointed out, in the case of the butadiene derivative, n is 0. In the case of diisobutenyl dioxide R" is CH -CH and n is 1. In another example previously referred to R" is CH -OCH' and n' is 1.

However, for practical purposes the only diepoxide available in quantities other than laboratory quantities is a derivative of glycerol or epichlorohydrin. This particular diepoxide is obtained from diglycerol which is largely acyclic diglycerol, and epichlorohydrin or equivalent thereof in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative, one could start with any one of a number of glycols or polyglycols and it is more convenient to include as part of the terminal oxirane ring radical the oxygen atom that was derived from epichlorohydrin or, as might be the case, methyl epichlorohydrin. So presented the formula becomes:

In the above formula R is selected from groups such as the following:

It is to be noted that in the above epoxides there is'a complete absence of (a) aryl radicals and (b) radicals in which or more carbon atoms are united in a single uninterrupted single group. R is inherently hydrophile in character as indicated by the fact that it is specified that the precursory diol or polyol OHROH must be watersoluble in substantially all proportions, i. e., water miscible.

Stated another way, what is said previously means that a polyepoxide such as is derived actually or theoretically, or at least derivable, from the diol HOROH, in which the oxygen-linked hydrogen atoms were replaced by Thus, R(OH),,, where n represents a small whole number which is 2' or more, must be water-soluble. Such limitation excludes polyepoxides if actually derived or theoretically derived at least, from water-insoluble diols or wateriusoluble triols or higher polyols. Suitable polyols may contain as many as 12 to 20 carbon atoms or thercabouts.

Referring to a compound of the type above in the formula in which R is C H (OH) it is obvious that reaction with another mole of epichlorohydrin with appropriate ring closure would produce a triepoxide or, similarly, if R happended to be C H (OH)OC H (OH), one could obtain a tetraepoxide. Actually, such procedure generally yields triepoxides, or mixtures with higher epoxides and perhaps in other instances mixtures in which diepoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free from aryl groups and also free from any radical having 5 or more carbon atoms in an uninterrupted chain. This particular diglycidyl ether is obtained by the use of epichlorohydrin in such a manner that approximately 4 moles of epichlorohydrin yield one mole of the diglycidyl ether, or, stated another way, it can be considered as being formed from one mole of diglycerol and 2 moles of epichloro-hydrin so as to give a molecular weight of approximately 370 and approximately 2 epoxide groups per molecule. series of subsequent examples this particular diglycidyl ether is, used, although obviously any of the others previously described would be just as suitable. For convenience, this diepoxide will be referred to as diglycidyl ether A. Such material corresponds in a general way to the previous formula.

Using laboratory procedure we have reacted diethyleneglycol with epichlorohydrin and subsequently with alkali so as to produce a product which, on examination, corresponded approximately to the following compound:

The molecular weight of the product was assumed to be 230 and the product was available in laboratory quantities only. For this reason, the subsequent table referring to the use of this particular diepoxide, which For this reason in the first of a til) will be referred to as diglycidyl ether B, is in grams instead of pounds.

Probably the simplest terminology for these polyepoxides, and particularly diepoxides, to differentiate from comparable aryl compounds is to use the terminology epoxyalkanes and, more particularly, polycpoxyalkanes or diepoxyalkanes. The difficulty is that the majority of these compounds represent types in which a carbon atom chain. is interrupted by an oxygen atom and, thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a heterocyclic ring. The principal class properly may be referred to as polyepoxypolyglycerols, or diepoxypolyglycerols.

Other examples of diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of combining erythritol with a carbonyl compound, such as formaldehyde or acetone so as to form the 5-membered ring, followed by conversion of the terminal hydroxyl groups into epoxy radicals.

See also Canadian Patent No. 672,935.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula OH OH OH H r H1 0 C H H R R n R In the above formula 71 represents a small whole number varying from 1 to 6, 7, or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms, such as butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance paraphenylphenol, one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and non-oxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic nonhydroxylated secondary amine as specified, following 9 the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

The basic nonhydroxylated amine may be designated thus:

RI HN In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. stance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

on on on UO R R n R acid as a catalyst, such strong acid should be neutralized.

Similarly, if a strong base is used as acatalyst it is preferable that the base be neutralized although we have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much a few l0ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resinv neutral.

Certain side reactions may take place. For in- In preparing resins one does not get a single polymer, ire one having just 3 units, or just 4 units, or just 5 units,'or just 6 units, etc. it is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than these which are lowest in price and most readily available commercially. I For purposes of convenience suitable resins are characterized in, the following table:

Table l E R Mfol. x- 0 res ample R ef g derived n molecule number frorn (based on n+2) Tertiary butyl Para.-.. 3. 5 882. 5

Secondary butyl Ortho... 3. 5 882. 5 Tertiary amyl Para 3. 5 959. 5 Mixed secondary Ortho... 3. 5 805. 5

and tertiary amyl. Propyl 3. 5 805. 5 Tertiary hexyl 3. 5 1, 036. 5 Octyl.-. 3. 5 1, 190. 5 Nony 3. 5 1. 267. 5 Decyl 3. 5 1, 344. 5 Dodecyl 3. 5 1, 498. 5 Tertiary butyl. 3. 5 V 945. 5

Tertiary amyL 3. 5 1, 022. 5 on 3. 5 t 1, 330. 5 Tertiary butyl 3. 5 1, 071. 5

Tertiary amyl do 3. 5 1, 148. 5 Nonyl do n 3. 5 1.4565 Tertiary bntyl do Propional- 3. 5 1,008.5 dehyde.

Tertiary amyl ...do. o 3.5 1,085. 5 Non dn dn 3.5 1, 393. 5 Tertiary butyl --d0-. Formal- 4. 2 996. 6

dehyde 21c Tertiary amyl do. 0 4.2 1, 083.4 on dn dn 4.2 1, 430.6 Tertiary butyl 4. 8 1, 094. 4 Tertiary amyl. 4. 8 1, 189. 6 No 4.8 1, 570. 4 1.5 604. 0 1. 5 653.0 1. 5 688.0

1. 5 786.0 1. 5 835.0 1 do 2.0 986.0 dehyde 32a Nonyl do o 2.0 1, 028.0 3311 myl do do 2. 0 860. 34a Buty Formal- 2. 0 636.

dehyde 35a Amyl. dndn 2.0 692. 0 till! Hexy (in do 2. O 748. 0

PART 3 Y As has been pointed out previously, the amine herein employed as a reactant is a basic secondary monoamine, and preferably a strongly basic secondary monoamine, free from hydroxyl groups whose composition is indicated thus: 7

in which R represents a monovalent alkyl, alicyclic, arylalkyl radical and may be heterocyclic'in a few instances as in the case of piperidine and a secondary amine derived from furfurylamine by methylation or ethylation, or a similar procedure.

Another example of a heterocyclic amine is, of course, morpholine.

The secondary amines most readily available are, of course, amines such as dimethylamine, methylethylamine, diethylamine, dipropylamine, ethylpropylamine, dibutylamine, diamylamine, dihexylamine, dioctylamine, and dinonylamine. Other amines include bis(l,3-di'- methyl-butyl)amine. There are, of course, a variety of primary amines, which can be reacted. withan alkylating agent such. as, dimethyl sulfate, diethyl sulfate, an alkyl bromide, an ester of sulfonic acid, etc., to produce suitable amines within the herein specified limitations. For example, one can methylate alpha-methyl-benzylamine, or benzylamine itself, to produce a. suitable reactant. Needless to say, one can use secondary amines such as dicyclohexylamine, dibutylamine; oramines containing one cyclohexyl group and one alkyl group, orone benzyl group and one alkyl group, such as ethylcyclohexyl amine, ethylbenzylamine, etc.

Another class of amines which: are particularly desirable for the reason that they introduce a definite hydrophile effect by virtue of an ether linkage, or repetitious ether linkage, are certain basic polyether amines of the formula [EKG 03 5):}

in which at is a small whole number having a value of 1 or more, andmay be as much as or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m' represents a number (I to l, with the proviso that the sum ofm plus m equals 2; and R. has its prior significance, particularly as a hydrocarbon radical.

Examples of such compounds are:

Other somewhat similar secondary amines are those of the composition.

as described in U. S. Patent No. 2,375,659 dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other amines can be obtained from products which are sold in the open market, such as maybe obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or, for that matter, amines of the kind described in U. 8'. Patent No. 2,482,546, dated. September 20; l949,'.to:Kaszuba, providedtthere is noinegative group or halogen attached to' the phenolic nucleus- Examples include the following: beta-phenoxyethylamine; gamma-phenoxypropylamine, beta-pheuoxyalpha-methylethylamine, and beta-phenoxypropylamine.

Other suitable amines are the kind described in British Patent No. 456,517 and may be illustrated by PART 4- The products obtained by the herein described processes employed inthe manufacture of the condensation product represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult toactually depict the final product of the cogeneric. mixture except in. terms of the process itself.

Previous reference-has'been -made' to the fact that the procedure herein employed is comparable, in: a general way, ,to that. which:v corresponds to. somewhat similar derivatives made either; from: .ph'enolsiast differentiated 12 fromaresin, or in the manufacture. of phenolamine-aldehyde resin; or elase from a particularly selected resin. and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heat reactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a singlephase system, and since temperatures up to C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been. said previously, in light of subsequent examples, However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at ordinary or higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient touse a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here-included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyll alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively non-volatile solventsuch as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in an oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difficult perhaps to add a solid material instead of. the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over 150C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such" as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the'most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation?; and the third factor is this, (c) is an effort to be made to purify the reaction mass-by the usual procedure as, for example, a waterwash to remove the water-soluble unreacted formaldehyde, if any, or a water-wash torernove any unreactcd low molal soluble-amine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, we have found xylene the most satisfactory solvent.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the'present procedure. There is no objective, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, We are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, than the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibi ity as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. n the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent No. 2,499,368. After the resin is in complete solution the amine is added and stirred. Depending on the amine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resinsolution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that l V perature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale it there is any difiiculty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over.

Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difficulties are involved. We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction has proceeded as far as one can reasonably expect at a low temperature; for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or 5 hours, or at the, most, up to 10-24 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts as required; The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of amine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about C., and generally slightly above 100 C., and below C., by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reactionmass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional mariner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary amine and 2 moles of formaldehyde. In some instance we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage 'in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess 'of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted amine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration: i

7 Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 1a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3% phenolic nuclei, as the value for rt which excludes the two external nuclei, i. e., the resin'was largely a mixture having 3 nuclei and 4 nuclei, excluding the two external nuclei or 5 and 6 overall nuclei. 'The resin so obtained in a neutral state had a lightamher color. 882 grams ofthe resin identified as 1a, preceding, were powdered and mixed with an equal weight of xylene, i. e., 882 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately C. to C., and 146 grams of diethylamine added. The mixture was stirred vigorously and formaldehyde added slowly. The formaldehyde was used as a 37% solution and 162 grams were employed, which were added in about 2 /2 hours. The mixture was stirred vigorously and kept within a temperature range of 30 to 45 C. for about 20 hours. At the end of this period of time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from 2 to 3 hours after refluxing was started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 145 C., or slightly higher. The mass was kept at this higher temperature for about 4 hours and reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene and the residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall time for the reaction was about 30 hours. Time can be reduced by cutting low temperature period to approximately 3 to 6 hours.

Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is 16 basic and thus one need not add the usual catalysts which are used to promote such reactions. Generally speaking, the reaction will proceed at a satisfactory rate under suitable conditions without any catalyst at all.

Employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials such as caustic soda, caustic potash, sodium methylate, etc. Other catalyst may be acidic in nature and are of the kind characterized by iron and tin chloride. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. If for any reason the reaction did not proceed rapidly enough with the diglycidyl ether or other analogous reactant, then a small amount of finely divided caustic soda or sodium methylate could be employed as a catalyst. The amount generally employed would be 1% or 2%.

It goes wtihout saying that the reaction can take place in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar others, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are to be rendered solvent-free and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, thus xylene or an aromatic petroleum will serve.

Example 10 The product was obtained by reaction between the diepoxide previously designated as diepoxide A, and condensate 1b. Condensate lb was obtained from resin 11:. Resin 1a was obtained from tertiary butylphenol and formaldehyde. Condensate lb employed as reactants resin 1a and diethylamine. The amount of resin employed was 882 grams; the amount of diethylamine employed was 146 grams; the amount of 37% formaldehyde employed was 162 grams, and the amount of solvent employed was 882 grams. All this has been described preillustrated by 24 examples m Table II. vlously.

Table II Strength of Reac- Reac- Max. Ex. Resin Amt, Amine used and amount tormalde- Solvent used tion tlon distill. N0. used grs. hyde 50111. and amt. temp., time, temp.,

and amt. 0. hrs. C.

882 Dlethylamine, 146 grams; 37%, 162 g Xylene, 882 g." 20-25 30 150 480 Dlethylamine, 73 grams 37%, 81 g Xylene, 480 g.-- 22-30 24 152 633 do 30%, g--- Xylene, 633 g. 21-24 as 147 441 Dlbutylamine, 129 grams 37%, 81 g Xylene, 441 g. 25-37 32 149 480 do do Xylene, 430 g. 20-24 35 149 633 d0 Xylene, 683 g. 18-23 24 150 882 Morphol ne, 174 grams.-. Xylene. 882 g 20-26 35 480 Morphollne, 87 grams. Xylene, 480 g--- 19-27 24 156 90... San". 633 do Xylene, 633 g 20-23 24 147 101) 1111.. 473 Dloctylamlne (di-2-ethylhexylamine) 117 grnms Xylene, 473 g 20-21 38 148 1112--.. 12m". 511 do Xylene, 511 g... 19-20 30 145 l2b 1311---- 665 ..-.-do Xylene, 665 20-26 24 130.- 1a... 441 (CzHaOCzHrOCzHOzNH, 250 grams Xylene, 441 g. 20-22 31 147 14b 3a.--.- 48 --.d 1 ,,do Xylene, 480 20-24 36 148 37%, 81 g Xylene, 595 g". 23-28 25 145 -do Xylene, 441 g- 21-28 24 151 Xylene, 480 g- 20-24 24 150 Xylene, 511 g. 20-22 25 140 Xylene, 498 g, 20-25 24 140 Xylene, 542 g 28-38 30 142 21b ..d0 Xylene, 547 g 25-30 20 1 8 2211-- m" 4 1 (GHKOOH2CHZCH2CH2CH2CHZ)ZNH, 245 grams Xylene, 441 g 20-22 28 143 23b 24a. 595 .do Xylene, 595 g 18-20 25 6 11--" 391 (CHKOOH20H2CH2CH2CH2CH2)2NH, 98 grams 30%, 50 g Xylene, 391 g--- 19-22 24 14s PART 5 Cognizance should be taken of one particular feature in connection with the reaction involving the polyepoxide and the amine condensate and that is this; the amine- The solution of the condensate in xylene was adjusted to a 50% solution. In this particular instance, and in practically all the others which appear in a subsequent table, the examples arecharacterized by the fact that no modified phenol-aldehyde resin condensate is invariably 75 alkaline catalyst was added. The reason is, of course,

' examine the physical properties.

that the condensate as such is strongly basic. If desired, a small amount of an alkaline catalyst could be added, such as finely powdered caustic soda, sodium methylate, etc. If such alkaline catalyst is added it may speed up the reaction but it also may cause an undesirable reaction, such as the polymerization of a diepoxide.

In any event, 105 grams of the condensate dissolved in 105 grams of xylene were stirred and heated to 106 C., 18.5 grams of the diepoxide previously identified as A and dissolved in an equal weight of xylene were added dropwise. The initial addition of the xylene solution carried the temperature to about 108 C. The remainder of diepoxide was added during approximately an hours time. During this period of time the reflux temperature rose to about 125 C. The product was allowed to reflux at a temperature of about 130 C. using a phaseseparating trap. A small amount of xylene Was removed by means of a phase-separating trap so the refluxing temperature rose gradually to about a maximum of 185 C. The mixture was refluxed at 185 C. for approximately 3 hours. Experience has indicated that this period of time was sufficient to complete the reaction. At the end of the period the xylene which had been removed during the reflux period was returned to the mixture. A small amount of material was withdrawn and the xylene evaporated on the hot plate in order to The material was a dark red viscous semi-solid. It was insoluble in water, it was insoluble in 5% gluconic acid, and it was soluble in xylene, and particularly in a mixture of 80% xylene and 20% methanol. solved in an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and particularly in a xylenemethanol mixed solvent as previously described, with or without the further addition of a little acetone.

The procedure employed of course is simple in light of what has been said previously and in efiect is a procedure similar to that employed in the use of glycide or methylglycide as oxyalkylation agents. See, for example, Part 1 of U. S. Patent No. 2,602,062, dated July 1, 1952, to De Groote.

Various examples obtained in substantially the same manner are enumerated in the following tables:

However, if the material was dis- Table V Probable Resin conggf iFg Amt. of Amt. of number of 5 Ex. N o. densaite rectio'n product, solvent hydroxyls use grs. grs. per mo eproduct Gale Table VI Resin congf gl g Amt. of Amt. of $5112. 3: 0 1 Ex. No. densaite rea'ctio'n product, solvent, hydroxyls use grs. grs. per mo eproduet cule At times We have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethyl ether of ethyleneglycol may be employed.

amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling solvent such as benzene, or usebenzene entirely. Also, we have found it desirable at times to use slightly Table III Oon- Time Diep- Max. 4 3 :5 5 oxide z 212 gg g 25$? temp Color and physical state used used hrs.

A 18. 5 123. 5 2:1 4 185 Brown viscous semisolid 124 A 18. 5 142. 5 2:1 4 180 D0. 108 A 18. 5 126. 5 2:1 4 188 D0. A 13. 5 134. 5 2:1 4 178 Do. A 18. 5 138. 5 2:1 4 190 Do. 159 A 18. 5 177. 5 2: 1 4. 5 185 Do. 141 A 18. 5 159. 5 2: 1 4. 5 182 D0. 177 A 18.5 195. 5 2:1 4. 5 188 D0. 164 A 18. 5 182. 5 2:1 4. 5 180 Do. 173 A 18. 5 191. 5 2:1 4. 5 192 Do.

Table IV Con- Time Drep- Max 33 5 oxide 5 2" 23 22%? 25:3 te mp Color and physical state used used hrs.

105 B 11 116 2:1 4 175 Brown .viscous semi-solid 124 B 11 2:1 4 175 D0. 108 B 11 119 2: 1 4 180 D0. 116 B 11 127 2:1 4 182 D0. 120 B 11 131 2: 1 4 178 D0. 159 B 11 2:1 4 182 D0. 141 B 11 152 2:1 4 185 D0. 177 B 11 188 2:1 4 178 D0. 164 B 11 2:1 4 183 Do. 173 B 11 184 2:1 4 D0.

Solubility in regard -to all these compounds was substantially similar to that which was described in Example 10.

Another procedure which is helpful is to reduce the less than apparently the theoretical amount of diepoxide, for instance 90% or 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true molecular weight by several percent.

Previously the condensate has been depicted ina simplified form which, for convenience, may be shown thus:

(Amine)CH (Resin) CH (Amine) Following such simplification the reaction product with a polyepoxide and particularly a diepoxide, would be indicated thus:

[(Amine) CHflResin) CH:(A1111J16)] /D. G .E. [(Amine) C H:(Resi.n) C H (Amine)] in which D. G. E. represents a diglycidyl ether as specified. If the amine happened to have more than one reactive hydrogen, as in the case of a hydroxylated amine or polyamine, having a multiplicity of secondary amino groups it is obvious that other side reactions could take place as indicated by the following formulas:

[(Amine) CHz(Amine)] [D.G.E.]

KAmine) GH:(Amine)] [(Resin) CH:(Resin)] [(Resln) H:(Resin)] [(Amine) CH;(Amine)] All theaboveindicates the complexity of the reaction product obtained after treating the amine-modified resin condensate with a polyepoxide and particularly diepoxide as herein described.

PART 6 The preparation of the compounds or products described in Part Sypreceding, involves an oxyalkylating agent, to wit, a polyepoxide and usually a diepoxide. The procedure described in the present part is a further oxyalkylation step but involves the use of a monoepoxide or the equivalent. The principle difference is only that while polyepoxides are invariably nonvolatile and can be reacted under a condenser, at least numerous monoepoxides and particularly ethylene oxide, propylene oxide, butylene oxide, etc. involve somewhat different operating conditions. Glycide and methylglyci-de react under practically the same conditions as the polyepoxides. Actual,- ly, for purpose of convenience, it is most desirable to conduct the previous reaction, i. e., the one involving the polyepoxide, in equipment such that subsequent reaction with monoepoxides may follow without interruption. For this reason considerable is said in detail as to oxyethylation, etc.

Although ethylene oxide and propylene oxide may re.- present less of a hazard than glycide, yet these reactants should be handled with extreme care. Onesuitable procedure involves the use of propylene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the appropriate resin condensate in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the selected resin condensate dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hy dr ophile properties, are obtained, if not previously present to the desired degree. Indeed, hydrophile character can be reduced or balanced by use of some other oxide, such as propylene oxide or butylene oxide. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final product may contain some unreaeted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation in any suitable manner. See article entitled .Ethylene Oxide Hazards and Methods of Handling,-Industrial and Engineering Chemistry, volume 42, No. 6, June 1950, pp. 1251-1258. Other procedures can be employed as, for example, that described in U. S. Patent No. 2,586,767, dated February 19, 1952, to Wilson.

The amount of monoepoxides employed may be as high as 50 parts of monoepoxide for one part of monoepoxide treated amine-modified phenol-aldehyde condensation product.

Example 1D The polyepoxide-derived oxyalkylation-susceptible compound is the one previously designated as 1c. Polyepoxi-de-derived condensate 1c was obtained, in turn, from condensate 2b and diepoxide A. Reference to Table II shows the composition of condensate 21). Table II shows it was obtained from resin 5a, diethylamine and formaldehyde. Table I shows that resin 5a was obtained from tertiary amylphenol and formaldehyde.

For purpose of convenience, reference herein and in the tables to the oxyalkylation-susceptible compound will be abbreviated in the table heading as OSC; reference is to the solvent-free material since, for convenience, the amount of solvent is noted in a second column. Actually, part of the solvent may have been present and in practically every case was present in either the resinification process or the condensation process, or in treatment with a polyepoxide. In any event, the amount of solvent present at the time of treatment with a monoepoxide is indicated, as stated, on a solvent-free basis.

12.35 pounds of the polyepoxide-derived condensate were mixed with 12.40 pounds of solvent (xylene in this series), along with one pound of finely powdered caustic sodas as a catalyst. The reaction mixture was treated with 6.25 pounds of ethylene oxide. At the end of the reaction period the molal ratio of oxide to initial compound was approximately 28.5 to one, and the theoretical molecular weight was approximately 3700.

Adjustment was made in the autoclave to operate at a temperature of about C. to C., and at a pressure of 10 to 15 pounds per square inch.

The time regulator was set so as to inject the oxide in approximately 30 minutes and then continue stirring for a half-hour longer simply as a precaution to insure complete reaction. The reaction went readily and, as a matter of fact, the ethylene oxide probably could have been injected in 15 minutes instead of a half-hour and the subsequent time allowed to insure completion of reaction may have been entirely unnecessary. The speed of reaction, particularly at low pressure, undoubtedly was due in a large measure to the excellent agitation and also to the comparatively high concentration of catalyst.

A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned, and also for the purpose of making some tests on various oil. field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data or sub sequent data, or in data reported in tabular form in subsequent Tables VII, VIII and IX.

The size of the autoclave employed was 35 gallons. In innumerable oxyalkylations we have withdrawn :1 substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a ditferent oxide. 7

21 Example 2D This simply illustrates further oxyalkylation of Example 1D, preceding. The oxyalkylation-susceptible compound 10 is the same as the one used in Example 1D,

22 element was only one-half hour because considerably less oxide was added.

Example'3D The oxyalkylation proceeded in the same manner as Preceding because it is merely a continuation In in Examples 1D and 2D. There was no added solvent subsequgilit tables, sugh as gable YII, the pxy y and no added catalyst. The amount of oxide added was l f g e f g m t e horlzomal P concealed .6.25 pounds. The total amount of oxide at the end of W t xizlnip e I: rlefers to oxyalkylatlon-susceptlble the stage was 18.75 pounds. The molal ratio of oxide ctzongnoun 1 c.1 ctuahly, one could refer ust as proper to condensate was 85 to 1. The theoretical molecular D at t Stage; 15 lmmatenal Whlch weight was approximately 6200, and the time period was es1g nat10ni1s used so long as 1t 1s understood such pr 45 minutes with temperature and pressure being the tree 1s use conslstently throughout the tables. In any same as in preceding Example 2D event, the amount of ethylene ox1de introduced was the same as before, to wit, 6.25 pounds. This meant the 15 Example 4D amount of oxide at the end of the stage was 12.50 pounds, The oxyalkylation was continued and the amount of and the ratio of oxide to oxyalkylation-susceptible oxide added was the same as before, to wit, 6.25 pounds. compound (molar basis) at the end was 37 to l. The. The amount of oxide added at the end of the reaction theoretlcal molecular weight was approximately 5000. was 25.0 pounds. There was no added solvent and no There was no added solvent. In other words, it remained added catalyst. Conditions as far as temperatures and the same, that 18, 12.40 pounds and there was no added pressure are concerned were the same as in previous catalyst. The entire procedure was substantially the examples. The time period was the same as before. same as in Example 1D, preceding. The reaction at this point showed modest, if any, In this, and in all succeeding examples the time and tendency to slow up. The molal ratio of oxide to pressure were the same as previously, to wit, 125 C. oxyalkylation-susceptible compound was 113.6 to 1. The to 130 C., and the pressure 10 to 15 pounds. The time theoretical molecular weight was about 7500.

Table VII Composition before Composition at and E Oxides Oxides Molal ratio X. N0. OSC, Cata- Sol- Cata-' Sol- Theo.

ex. 030, lyst, vent, 0S0, lyst, vent, EtO PrO BuO mol. No. lbs. EtO, PrO, BuO, lbs. lbs. lbs. EtO, PrO, BuO, lbs. lbs. to oxyto oxyto oxywt.

lbs. lbs. lbs. lbs. lbs. lbs. alkyl. alkyl. alkyl.

suscept. suscept. suseept. compd. compd. compd.

Theo. mol. wt.

BuO

alkyl.

555555555222 5555 555333333111uummmmmm MMOOOO 11111 111111111111.

PrO

Molal ratio EtO to oxyto oxyto oxyalkyl. alkyl. suscept. suscept. suseept. compd. compd. compd.

8 6 omzufiloainhnwnmoa-hlixmznn 5 25 14713692 13571544QQQQ%%%%%%%%3%%% 111 1 11 111111 Solvent, lbs.

Composition at end Catalyst, lbs

555555555555555555555555555555555555 1.111111LLLLLLLLLLLLLLLLLLLLLLLL.LLLLL BuO, lbs.

Oxides tttttttrrtrtaaaaaaatt 7 2 4 &taaL2 5 0 &

EtO, PrO,

lbs.

Table IX 080, lbs.

Sol-

lbs.

Cats.- lyst, vent,

lbs.

55.0555555555555555555555555555555555 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL BuO, lbs.

11111l999999666666000000777777999999 ZZZZZZQMQWQWQMQWQZZZZZZZZZZTZ 2 222222111111111111333333QQQQ4Q33333$ Oxides PrO, lbs.

Composition before EtO 080, lbs.

ex. No.

as. No. oso,

Example 5D Examples 37D through 54D were obtained by the use of The oxyalkylation was continued with the introduction 40 butylene of another 6.25 pounds of oxide. No added solvent was Referrmg Table VIII P P Y, 1t W111 be introduced and likewise no added catalyst was introduced. notefi that the Senes of eXamples begllmlflg Wlth 1E were The theoretical molecular weight at the end of the Obtalned, 111 mm, y use of both ethylene and P py oxides, using ethylene first; in fact, using Example 2D as the oxyalkylation-susceptible compound. This applies The time period was increased to one hour. to F F 1E through Snmlarly, series 19E through 36E involve the use of Example 6D both propylene oxide and ethylene oxide in which the The same procedure was followed as in the Pr vi u propylene oxide was used first, to wit, 19E was prepared examples without the addition of either more catalyst from 24D, a compound which was initially derived by The amount of oxide added was larger use of propylene oxide. than before, 110 Will, 18.75 pounds. The amount Of oxide Similarly, Examples 37E through 54E involve the use of ethylene oxide and butylene oxide, the ethylene oxide being used first. Also, these two oxides were used in butylene oxide was used first and then the ethylene oxide. Series 73E through 90E involve the use of propylene oxide and butylene oxide, butylene oxide being used first The same procedure as described in the previous and propylene oxide being used nextp examples Was p y in connection With a number In Series 1F through 18F the three oxides were used. of the other condensations described previously. All It will be noted in Example IF the initial compound was these data have been presented in tabular form in Tables 78E; Example 78E, in turn, was obtained from a com- VII through XII. pound in which butylene oxide was used initially and In substantially every case a 35-gallon autoclave, was then propylene oxide. Thus, the oxide added in the employed, although in some instances the initial oxyseries 1F through 6F was by use of ethylene oxide as ethylation was started in a 15-gallon autoclave and then indicated in Table IX. transferred to a 25-gallon autoclave, or at times to the Referring to Table IX, in regard to Example 19F it will be noted again that the three oxides were used and 19F was obtained from 60E. Example 60E, in turn, The catalyst used was finely was obtained by using butylene oxide first and then ethylene oxide. In Example 19F and subsequent ex- Referring to Tables VII, VIII and IX, it will be noted amples, such as 20F, 21F, etc. propylene oxide was added. that compounds 1D through 18D were obtained by the Tables X, XI and XII give the data in regard to the oxyalkylation procedure as far as temperature and presreaction was approximately 8700. The molal ratio of oxide to oxyalkylation-susceptible compound was 142.0 45

or more solvent.

at the end of the reaction was 50.0 pounds. The time required to complete the reaction was slightly more than P y, to 1% hOufS- t t e end of the reaction 55 the Series 55E through 72E, but in this latter instance the period the ratio of oxide to oxyalkylation-susceptible compound was 227 to 1, and the theoretical molecular weight was 12,500.

35-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene.

powdered caustic soda.

use of ethylene oxide, whereas Examples 19D through H 36D were obtained by the use of propylene oxide; and 75 sure are concerned and also give some data as to solubility of the oxyalkylation derivative in water, xylene and kerosene.

Referring to Table VII in greater detail, the data are as follows: The first column gives the example num- The tenth column shows the amount of ethylene oxide in at the end of the particular step.

Column eleven shows the same data for propylene oxide and column twelve shows data for butylene oxide. For

bers, such as 1D, 2D, 3D, etc. etc.; the second column 5 obvious reasons these can be ignored in the series 1D gives the oxyalkylation-susceptible compound employed through 18D.

which, as previously noted in the series 1D through 6D, Column thirteen shows the amount of the catalyst at is Example 10, although it would be just as proper to the end of the oxyalkylation step, and column fourteen say that in the case of 2D the oxyalkylation-susceptible shows the solvent at the end of the oxyalkylation step. compound was 1D, and in the case of 3D the oxyalkyla- 10 The fifteenth, sixteenth and seventeenth columns are tion-susceptible compound was 2D. Actually, reference concerned with molal ratio of the individual oxide to the is to the parent derivative for the reason that the figure oxyalkylation-susceptible compound. Data appears only stands constant and probably leads to a more convenlent in column fifteen for the reason, previously noted, that presentation. Thus, the third column indicates the no butylene or propylene oxide were used in the present expoxide-derived condensate previously referred to. instance.

The fourth column shows the amount of ethylene oxide The theoretical molecular weight appears at the end in the mixture prior to the particular oxyethylation step. of the table which is on the assumption, as previously In the case of Example 1D there is no oxide used but it noted, as to the probable molecular weight of the initial appears, of course, in 2D, 3D, and 4D, etc. compound, and on the assumption that all oxide added The fifth column can be ignored for the reason that during the period combined. This is susceptible to limiit is concerned with propylene oxide only, and the sixth tations that have been pointed out elsewhere, particularly column can be ignored for the reason that it is conin the patent literature. cerned with butylene oxide only. Referring now to the second series of compounds in The seventh column shows the catalyst which is invari- Table VII, to wlt, Examples 19D through 36D, the situaably powdered caustic soda. tion is the same except that it is obvious that the The eighth column shows the amount of solvent which oxyalkylating agent used was propylene oxide and not is xylene unless otherwise stated. ethylene oxide. Thus, the fourth column becomes a blank The ninth column shows the oxyalkylation-susceptible and tenth column becomes a blank and the fifteenth colcompound which in this series is the polyepoxide-derived umn becomes a blank, but column five, which previously condensate. was a blank in Table VII, Examples 1D through 18D,

Table X M as. Max. Solubility Ex. temp., pres, Time, No. 0. p. s. i. hrs.

Water Xylene Kerosene -130 10-15 Insoluble Insoluble. 125-130 10-15 Emulsifiable" D0. 125-130 10-15 Do. 125-130 1015 D0. 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 Do.

10-15 Do. 125-130 1045 Do. 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 Do. 125-130 10-15 Do. 125-130 1015 Do. 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 Dispersiblc 125-130 10-15 uble. 125-130 10-15 Insoluble. 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 Do. 125-130 10-15 Soluble. 125-130 1015 Do. 125-130 10-15 Insoluble 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 Soluble. 125-130 10-15 Do -150 10-15 Insoluble 145-150 10-15 D0. 145-150 10-15 Dispersible 145-150 10-15 olublc. 145-150 10-15 D0. 145-150 1015 D0. 145-150 10-15 Insoluble 145-150 10-15 Do. 145-150 10-15 Soluble. 145-150 10-15 D0. 145-150 10-15 Do. 145-150 10-15 Do. 145-150 10-15 Insoluble 145-150 10-15 Do. 145-150 10-15 Do. 145-150 10-15 Soluble. 145-150 10-15 D0. 145-150 10-15 D01 29 now carries data as to,the amount of propylene oxide present at the beginning of the reaction. Column eleven carries data as to the amount of propylene oxide present at the end of the reaction, and column sixteen carries data as to the ratio of propylene oxide to the oxyalkylation-susceptible compound. In all other instances the various headings have the same significance as previously.

Similarly, referring to Examples 37D through 54D in Table VII, columns four and five are blanks, columns ten and eleven are blanks, and columns fifteen and sixteen are blanks, but data. appear in column six as to butylene oxide present before the particular oxyalkalation step. Column twelve gives the amount of butylene oxide present at the end of the step, and column seventeen Table XI Max. Max. Solubility Ex. temp., pres Time, No. 0. p. s. i. hrs.

Water Xylene Kerosene 10-15 Emulsifiable. Insoluble. 10-15 do Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 Soluble. 10-15 Insoluble 10-15 D0. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Soluble. 10-15 Do. 10-15 Insoluble. 10-15 Do. 10-15 -Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 Do. 1015 Do. 10-15 Soluble. 10-15 D0. 10-15 Do. 10-15 Insoluble. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 D0, 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 Dc. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Soluble. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 Insoluble 10-15 Do. 10-15 Soluble. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Insoluble 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Soluble. 10-15 Do.

31 gives the ratio of butylene oxide to oxyalkylation-susceptible compound.

Table VIII is in essence the data presented in exactly the same way except the two oxides appear, to wit, ethylene oxide and propylene oxide. This means that there are only three columns in which data does not appear, all three being concerned with the use of butylene oxide. Furthermore, it shows which oxide was used first by the very fact that reference to Example 1E, in turn, refers to 5D, and also shows that ethylene oxide was present at the very first stage. Furthermore, for ease of comparison and also to be consistent, the data under Molal Ratio in regard to ethylene oxide and propylene oxide goes back to the original diepoxide-derived condensate 10. This is obvious, of course, because the figures 142.0 and 42.6 coincide with the figures for 5D derived from 1C as shown in Table VII.

In Table VIII (Examples 19E through 36E) the same situation is involved except, of course, propylene oxide is used first and this, again, is perfectly apparent. Three columns only are blank, to wit, the three referring to butylene oxide. The same situation applies in examples such as 37B and subsequent examples where the two oxides used are ethylene oxide and butylene oxide, and the table makes it plain that ethylene oxide wasused first. Inversely, Example 55B and subsequent examples show the use of the same two oxides but with butylene oxide being first as shown on the table.

Example 73E and subsequent examples relate to the use of propylene oxide and butylene oxide. Examples beginning with 1F, Table IX, particularly 2F, 3F, etc., show the use of all three oxides so there are no blanks as in the first step of each stage where one oxide is missing. It is not believed any further explanation need be offered in regard to Table IX.

As previously pointed out certain initial runs using one oxide only, or in some instances two oxides, had to be duplicated when used subsequently for further reaction. It would be confusing to refer to too much detail in these various tables for the reason that all the data appear in considerable detail and is such that all results can be readily shown.

Reference to solvent and amount of alkali at any point takes into consideration the solvent from the previous step and the alkali left from this step. As previously pointed out, Tables X, XI and XII give operating data inconnection with the entire series, comparable to what has been said inregard to Examples 1D through 6D.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the Tables. If desired, the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indifierent oxyalkylation, i. e., not attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides, just mentioned, or a combination of both of them.

The same would be true in regard to a mixture of ethylene oxide and butylene oxide, or butylene oxide and propylene oxide.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber, or a straw color, or even a pale straw color. The reason is primarily that no efiort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariable yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use a darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter Table XII Max. Max. Solubility Ex. temp., pres., Time, No. C. p. s. 1. hrs.

Kerosene 10-15 Soluble.

10-15 Do. -130 10-15 do .s.. D0. 125-130 10-15 Emulsifiable. Insoluble 125-130 10-15 do D 125-130 10-15 do.. Do. -125 10-15 Insoluble Soluble. 125-130 10-15 do D0. 125-130 10-15 Emulsifiable- Do. 125-130 10-15 (1 Insoluble 125-130 10-15 Do. 125-130 10-15 Do. 150-125 10-15 Soluble. 125-130 10-15 D0. 125-130 10-15 Insoluble 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 D0. 150-125 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 Do. 150-125 10-15 Do. 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 Do. 125-130 10-15 D0. 150-125 10-15 D0. 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 D0, 125-130 10-15 Do. 125-130 10-15 D0.

the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can be decolorized by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses, there is no justification for the cost of bleaching the product.

'Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per se are alkaline due to the presence of a basic nitrogen, the removal of the alkaline catalyst is somewhat more difficult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the presence of the alkali unless it is objectionable or else add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

PART 7 As to the use of conventional demulsifying agents, reference is made to U. S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and efiect to the instant process, noting only that where reference is made to Example 13b in said text beginning in column 15 and ending in column 18, reference should be to Example 1E, herein described.

PART 8 The products, compounds or the like, herein described can be employed for various purposes and particularly for the resolution of petroleum emulsions of the waterin-oil type as described in detail in Part 7, preceding.

, Such products can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cation-active materials. Instead of an imine one may employ what is somewhat equivalent material, to wit, a dialkylaminoepoxypropane of the structure.

O HG/ R IEULN/ wherein R and R" are alkyl groups.

It is not necessary to point out that, after reaction with a reactant of the kind described which introduces a basic nitrogen atom, the resultant product can be employed for the resolution of emulsions of the water-in-oil type as described in Part 7, preceding, and also for other purposes described hereinafter.

Referring now to the use of the products obtained by reaction'with a polyepoxide and certain specified oxyalkylatedproducts obtained in the manner described in Part 6, preceding, it is to be noted that in addition to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and waxes, as ingredients in the laundering, scouring, drying, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for :more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification, etherization, etc.

The oxyalkylated derivatives may be used as valuable radditives to lubricating oils, both those derived from petroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous and non-aqueous types. They may be used in connection with other procesies where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the sur rounding strata, and particularly in secondary recovery operations using aqueous flood water's. These derivatives also are suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initial resin, the particular monoepoxide selected, and the ratio of monoepoxide to resin, together duced between the insoluble reactants. Furthermore; such products can be used for a variety of other purposes, including use as corrosion inhibitors, defoamers, asphalt additives, and at times even in the resolution of oil-inwater emulsions. They serve at times as mutual solvents promoting a homogeneous system from two otherwise insoluble phases.

The products herein described can be reacted with polycarboxy acids such as phthalic acid, or anhydride, maleic acid or anhydride, diglycolic acid, and various tricarboxy and tetracarboxy acids so as to yield acylated derivatives particularly if one employs one mole of the polycarboxy acid for each reactive hydroxyl radical present in the final polyepoxide treated product. Thus, one obtains a comparatively large molecule in which there is a plurality of carboxyl radicals. Such acidic fractional esters are suitable for the resolution of petroleum emulsions of the water-in-oil type as herein described.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

l. A 3-step manufacturing method involving (1) con. densation; (2) oxyalkylation with a polyepoxide; and (3) oxyalkylation with a monoepoxide; said first step being that of (A) condensing (a) a fusible, non-oxygenated organic solvent-soluble, water-insoluble, phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6, position; (b) a basicv nong hydroxylated secondary monoamine having up to 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufliciently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from'the process be heat stable; followed as a second step by (B) reacting said resin condensate with nonaryl hydrophile polyepoxides containing two terminal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a water-soluble polyhydric alcohol by the radical said polyepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and.

characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free, from any radical. having more than 4 uninterrupted carbon atoms in a single chain; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the polyepoxide, and then completing the reaction by a third step of (C) reacting said polyepoxide-derived product with a monoepoxide; said monoepoxide being an alpha-beta alkylene oxide havingnot more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

2. The product obtained by the method described in claim 1.

3. A 3-step manufacturing method involving (1) condensation; (2) oxyalkylation with a'polyepoxide; and (3) oyxalkylationtwith a monoepoxide; said first step being that of (A) condensing (a) a fusible, non-oxygenated organic solvent-soluble, water-insoluble, phenolaldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol be ing of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6, position (b) a basic nonhydroxylated secondary monoamine having up to 32 carbon atoms in any group attached to the amino nitrogen atom, and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable followed as a second step by (B) reacting said resin condensate with nonaryl hydrophile polyepoxides containing at least two 1,2-epoxy rings and having two terminal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a watersoluble polyhydric alcohol by the radical said polyepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said polyepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below thepointi of pyrolysis;

and said reactiontbetween (A) and (B) being3conducted, below the pyrolytic point of the reactantsnandi the I'Bw sultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resinicondensate to l1 mole of the polyepoxide, and then completing the re-- action bya third step of (C) reactingj said polyepoxidederived product with a monoepoxide; said. monoepoxide being analpha-beta alkylene oxide having not more than, 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

4. A 3-step manufacturing method involving (1) condensation; (2) oxyalkylation with a polyepoxide; and (3) oxyalkylation with a monoepoxide; said: first step being that of (A) condensing, (a) a fusible, nonoxygenate'd organic solvent-soluble, water-insoluble, phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in thesubstantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated alphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic nonhydroxylated secondary monoamine having up to 32 carbon atoms in any group attached to the amino nitrogen atom, and (0) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable; followed as a second step by (B) reacting said resin condensate with nonaryl hydrophile diepoxides containing two terminal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a watersoluble polyhydric alcohol by the radical said diepoxides being free from reactive functional groups other than l,2-epoxy andhydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said diepoxides. being characterized by having present not more than 20 carbonatoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the diepoxide; and then completing the reaction by a third step of (C) reacting said diepoxide-derived product with a monoepoxide; said monoepoxide being an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

5. The method of claim 4 wherein the diepoxidotcom tains at least one ,reactivehydroxyl radical,

6. A 3-step manufacturing method involving 1) condensation; (2) oxyalkylation with a polyepoxide;'and (3) oxyalkylation with a monoepoxide; said first step being that of (A) condensing (a) a fusible, nonoxygenated organic solvent-soluble, water-insoluble, phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol.

being of the formula ous condensation product resulting from the process be heat-stable; followed as a second step by (B) reacting said resin condensate with a hydroxylated diepoxypolyglycerol containing two terminal 1,2-epoxy rings and having not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solventsoluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the'resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the diepoxide; and then completing the reaction by a third step of (C) reacting said diepoxide-derived product with a monoepoxide; said monoepoxide being an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butlene oxide, glycide and methylglycide.

7. The method of claim 6 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the precursory aldehyde is formaldehyde, and the total number of phenolic nuclei in the initial resin are not over 5.

No references cited. 

1. A 3-STEP MANUFACTURING METHOD INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A POLYEPOXIDE; AND (3) OXYALKYLATION WITH A MONOEPOXIDE; SAID FIRST STEP BEING THAT OF (A) CONDENSING (A) A FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AND ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 